JPH1180069A - Oxidation - Google Patents
OxidationInfo
- Publication number
- JPH1180069A JPH1180069A JP10192208A JP19220898A JPH1180069A JP H1180069 A JPH1180069 A JP H1180069A JP 10192208 A JP10192208 A JP 10192208A JP 19220898 A JP19220898 A JP 19220898A JP H1180069 A JPH1180069 A JP H1180069A
- Authority
- JP
- Japan
- Prior art keywords
- oxidation step
- chlorotoluene
- chlorobenzaldehyde
- electrochemical oxidation
- manganese salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【0001】本発明は酸化方法、特にクロロトルエンを
クロロベンズアルデヒドへ酸化するための方法に関す
る。[0001] The present invention relates to an oxidation method, in particular to a method for oxidizing chlorotoluene to chlorobenzaldehyde.
【0002】本発明によれば、第1の反応器の中でクロ
ロトルエン、好ましくは、オルトクロロトルエン(OC
T)またはパラクロロトルエン(PCT)を、酸化剤と
して第2の反応器の中で二価マンガン塩を電気化学的に
酸化することによって生成された三価マンガン塩を使用
して、化学的に酸化することを特徴とするクロロベンズ
アルデヒド、好ましくは、オルトクロロベンズアルデヒ
ド(OCB)またはパラクロロベンズアルデヒド(PC
B)の製造方法が提供される。According to the invention, chlorotoluene, preferably orthochlorotoluene (OCC), is provided in a first reactor.
T) or parachlorotoluene (PCT) is chemically converted using a trivalent manganese salt produced by electrochemically oxidizing a divalent manganese salt in a second reactor as an oxidizing agent. Chlorobenzaldehyde characterized by oxidation, preferably ortho chlorobenzaldehyde (OCB) or parachlorobenzaldehyde (PC
The manufacturing method of B) is provided.
【0003】マンガン塩の陰イオンは任意の無機陰イオ
ンたとえばリン酸塩陰イオンでありうる。しかしなが
ら、カソードとアノードの安定性、腐食および有機反応
体または生成物に対する攻撃などの点で工程上の問題を
最も少なくする陰イオンは硫酸塩陰イオンである。した
がって本発明の方法においては、酸化剤として硫酸マン
ガンを使用するのが好ましい。[0003] The anion of the manganese salt can be any inorganic anion, such as a phosphate anion. However, sulfate anions are the ones that minimize process problems in terms of cathode and anode stability, corrosion and attack on organic reactants or products. Therefore, in the method of the present invention, it is preferable to use manganese sulfate as the oxidizing agent.
【0004】酸化剤として硫酸マンガンを使用する好ま
しい態様におけるOCTのOCBへの化学的酸化は下記
の反応図式で示される:[0004] The chemical oxidation of OCT to OCB in a preferred embodiment using manganese sulfate as the oxidizing agent is illustrated by the following reaction scheme:
【化1】 Embedded image
【0005】二次反応において、OCT出発物質のいく
らかは下記のごとくオルトクロロ安息香酸(OCBA)
へ酸化されるであろう:[0005] In the secondary reaction, some of the OCT starting material is orthochlorobenzoic acid (OCBA) as follows:
Will be oxidized to:
【化2】 Embedded image
【0006】二価マンガン塩の三価マンガン塩への電気
化学的酸化は、硫酸塩を使用する好ましい態様の場合、
下記反応図式で示すことができる:The electrochemical oxidation of a divalent manganese salt to a trivalent manganese salt, in a preferred embodiment using a sulfate,
This can be illustrated by the following reaction scheme:
【化3】 Embedded image
【0007】Mn2( SO4)3 の生成はアノードで起こ
る。アノードで起こり得る二次反応は水からの酸素の発
生(2H2 O→4H+ +O2 +4e- )ならびにOC
T、OCBおよびOCBAの水和によるCO2 とCl2の
発生である。カソードで起こり得る二次反応は水素の発
生(2H+ +2e- →H2 )である。The formation of Mn 2 (SO 4 ) 3 occurs at the anode. A possible secondary reaction at the anode is the evolution of oxygen from water (2H 2 O → 4H + + O 2 + 4e − ) and OC
T, is the generation of CO 2 and Cl 2 due to hydration of OCB and OCBA. A possible secondary reaction at the cathode is the evolution of hydrogen (2H + + 2e − → H 2 ).
【0008】電気化学的酸化工程は硫酸中で、特に40
乃至70%の範囲の濃度を有する硫酸中で、より好まし
くは50乃至60%の範囲の濃度を有する硫酸中で都合
よく実施される。また、電気化学的酸化工程は70乃至
100℃の範囲の温度、より好ましくは85乃至100
℃、特に好ましくは85乃至95℃の範囲の温度で実施
するのが好都合である。The electrochemical oxidation step is carried out in sulfuric acid,
It is conveniently carried out in sulfuric acid having a concentration in the range of from 70 to 70%, more preferably in sulfuric acid having a concentration in the range of from 50 to 60%. In addition, the electrochemical oxidation step is performed at a temperature in the range of 70 to 100 ° C., more preferably 85 to 100
C., particularly preferably at a temperature in the range of from 85 to 95.degree.
【0009】電気化学的酸化工程の間の総マンガン塩の
濃度は電解質1リットルあたり2乃至6モルの範囲であ
り得、電解質1リットルあたり3乃至4モルの濃度が好
ましい。The concentration of the total manganese salt during the electrochemical oxidation step can range from 2 to 6 moles per liter of electrolyte, with a concentration of 3 to 4 moles per liter of electrolyte being preferred.
【0010】電気化学的酸化工程で使用されるアノード
材料とカソード材料は、好ましくは同種でありそして、
たとえば、ガラス質グラファイト、鉛、鉛合金、プラチ
ナ、パラジウムまたはルテニウムでコーティングされた
ジルコニウム、またはパラジウムまたはルテニウムでコ
ーティングされたタンタルでありうる。特に好ましいの
は銀を含有する鉛合金である。The anode and cathode materials used in the electrochemical oxidation step are preferably homogeneous and
For example, it can be vitreous graphite, lead, lead alloy, platinum, zirconium coated with palladium or ruthenium, or tantalum coated with palladium or ruthenium. Particularly preferred is a lead alloy containing silver.
【0011】電気化学的酸化工程は空気の雰囲気を備え
たセル内で実施するのが好都合である。すでに記載した
ように、電気化学的工程では爆発の可能性のある気体で
ある水素と酸素が発生するので、空気で希釈することが
爆発の危険を回避するために役立つ。これらの気体は痕
跡量の塩素を除去するため洗浄処理することができる。[0011] The electrochemical oxidation step is conveniently carried out in a cell provided with an air atmosphere. As already mentioned, the electrochemical process produces potentially explosive gases, hydrogen and oxygen, so dilution with air helps to avoid the risk of explosion. These gases can be cleaned to remove traces of chlorine.
【0012】電気化学的酸化工程のためには不活性材料
からつくられた任意の好都合な形状の電解セルを使用す
ることができる。好ましくは、電気化学的酸化工程は、
好ましくは並列配置された、複数の電解セルの電池の中
で実施される。二極型のセルが好ましく、その中でも良
好な循環と脱ガスを保証する手段を具備しているものが
特に好ましい。For the electrochemical oxidation step, any convenient shape of electrolytic cell made from an inert material can be used. Preferably, the electrochemical oxidation step comprises:
It is preferably carried out in a battery of a plurality of electrolysis cells arranged in parallel. Bipolar cells are preferred, among which those with means for ensuring good circulation and degassing are particularly preferred.
【0013】電気化学的酸化工程において付与される電
流密度は、たとえば、200乃至700mA/cm2であり得
る。300乃至500mA/cm2の電流密度が好ましい。The current density applied in the electrochemical oxidation step can be, for example, between 200 and 700 mA / cm 2 . A current density of 300 to 500 mA / cm 2 is preferred.
【0014】電気化学的酸化工程における二価マンガン
の三価マンガンへの転化率は高い。80%までの転化率
が容易に達成可能である。The conversion of divalent manganese to trivalent manganese in the electrochemical oxidation step is high. Conversions of up to 80% are easily achievable.
【0015】電気化学的酸化工程とは別途に実施される
化学的酸化工程に関しては、同じく硫酸中で実施するの
が好ましく、特に40乃至70%の濃度範囲、より好ま
しくは50乃至60%の濃度を有する硫酸中で実施する
のが好ましい。この化学的酸化工程は80乃至110℃
の範囲の温度、特に85乃至105℃の温度で実施する
のが好都合である。The chemical oxidation step which is carried out separately from the electrochemical oxidation step is also preferably carried out in sulfuric acid, particularly in the concentration range of 40 to 70%, more preferably in the concentration range of 50 to 60%. It is preferably carried out in sulfuric acid having This chemical oxidation step is 80-110 ° C
It is expedient to carry out at a temperature in the range of in particular 85 to 105 ° C.
【0016】化学的酸化工程中の総マンガン塩の濃度は
酸化反応媒質1リットルあたり2乃至6モルでありう
る。酸化反応媒質1リットルあたり3乃至4モルの範囲
が好ましい。酸化反応媒質は水性相(硫酸)、水性相に
懸濁された固体無機マンガン塩およびOCT、OCB、
OCBAを含む有機液体相を包含する。OCT以外の付
加的有機溶剤を使用する必要はない。The concentration of the total manganese salt during the chemical oxidation step can be from 2 to 6 moles per liter of oxidation reaction medium. The range is preferably 3 to 4 mol per liter of the oxidation reaction medium. The oxidation reaction medium is an aqueous phase (sulfuric acid), a solid inorganic manganese salt suspended in the aqueous phase and OCT, OCB,
Organic liquid phase comprising OCBA. It is not necessary to use additional organic solvents other than OCT.
【0017】化学酸化工程においては、クロロトルエン
のクロロベンズアルデヒドへの、好ましくはOCTのO
CBへの89%の転化率が容易に達成可能である。クロ
ロトルエンのクロロベンズアルデヒドへの転化の選択性
を最大にしそしてクロロ安息香酸の生成を最少にするた
めに、約30乃至50%の転化率が達成された時にクロ
ロトルエンのクロロベンズアルデヒドへの転化を中断す
るのが好ましい。本化学酸化工程ではクロロトルエン、
いくらかの水およびいくらかの電気エネルギーのみが消
費される。廃生成物は少量のクロロ安息香酸(クロロト
ルエンを基準にして約3%)と水素と痕跡量の塩素だけ
である。In the chemical oxidation step, chlorotoluene to chlorobenzaldehyde, preferably OCT
A conversion of 89% to CB is easily achievable. To maximize the selectivity of the conversion of chlorotoluene to chlorobenzaldehyde and minimize the production of chlorobenzoic acid, the conversion of chlorotoluene to chlorobenzaldehyde is interrupted when a conversion of about 30-50% is achieved. Is preferred. In this chemical oxidation process, chlorotoluene,
Only some water and some electrical energy are consumed. The waste products are only small amounts of chlorobenzoic acid (about 3% based on chlorotoluene), hydrogen and traces of chlorine.
【0018】化学酸化工程の反応生成物混合物から所望
のクロロベンズアルデヒドを分離する操作は任意の常用
方法によって実施することができる。たとえば、カラム
抽出装置が使用できる。有機相をアルカリ洗浄して痕跡
量の硫酸を除去し、そのあと蒸留してクロロベンズアル
デヒド生成物を未反応クロロトルエンから分離すること
ができ、その未反応クロロトルエンはそのあと化学的酸
化工程に再循環することができる。The operation of separating the desired chlorobenzaldehyde from the reaction product mixture in the chemical oxidation step can be carried out by any conventional method. For example, a column extraction device can be used. The organic phase can be washed with alkali to remove traces of sulfuric acid and then distilled to separate the chlorobenzaldehyde product from unreacted chlorotoluene, which is then recycled to the chemical oxidation step. Can circulate.
【0019】本発明の方法によって得られるクロロベン
ズアルデヒド、好ましくはOCBまたはPCBは公知化
合物でありそして広範な化学的最終製品、たとえば、香
料、蛍光増白剤、染料、紫外線吸収剤などのための中間
生成物として使用することができる。The chlorobenzaldehydes, preferably OCB or PCB, obtained by the process of the present invention are known compounds and intermediates for a wide range of chemical end products, such as fragrances, optical brighteners, dyes, UV absorbers and the like. It can be used as a product.
【0020】以下、本発明を実施例によってさらに説明
する。Hereinafter, the present invention will be further described with reference to examples.
【実施例】下記構成要素からなる電気化学的装置を組み
立てた:1.5リットル容量の反応器;循環ポンプ;鉛
アノードと鉛カソードを有し、そのアノードの表面積が
1平方デシメータである電気化学的セル。EXAMPLE An electrochemical device was constructed comprising the following components: a 1.5 liter reactor; a circulating pump; an electrochemical device having a lead anode and a lead cathode, the anode having a surface area of one square decimator. Cell.
【0021】装置にMnSO4・H2 O745gとH2 S
O4 (55%)1655gとからなる電解質2400g
を充填した。36アンペアの電流と3.1ボルトの電池
電圧を使用して85乃至90℃の温度で6.5時間電気
分解(電気化学的酸化)を実施したところMn2(SO4)
3 1704gが得られた。電流効率は55%であった。745 g of MnSO 4 .H 2 O and H 2 S
2400 g of electrolyte consisting of 1655 g of O 4 (55%)
Was charged. The electrolysis (electrochemical oxidation) was carried out at a temperature of 85-90 ° C. for 6.5 hours using a current of 36 amps and a battery voltage of 3.1 volts, and Mn 2 (SO 4 )
3 1704 g were obtained. The current efficiency was 55%.
【0022】得られたMn2(SO4)3 の懸濁物を強力撹
拌しながらOCT315gを含有する1.5リットル容
量の反応器に導入し、この混合物を105乃至110℃
の温度にサーモスタットで調温した。1.5時間の反応
時間後のMn3+のMn2+への転化率は95%を越えるも
のであった。The resulting suspension of Mn 2 (SO 4 ) 3 was introduced with vigorous stirring into a 1.5 liter reactor containing 315 g of OCT, and the mixture was heated to 105 ° -110 ° C.
The temperature was adjusted with a thermostat. After a reaction time of 1.5 hours, the conversion of Mn 3+ to Mn 2+ exceeded 95%.
【0023】反応後、反応混合物を傾瀉フラスコに移
し、そのフラスコの中で有機相を1時間かけて熱間傾瀉
することによって無機相から分離した。この分離効率は
99.0%であった。このあと、無機相を残留有機生成
物の濃度が400ppm 以下となるまでストリッピングし
て精製した。精製された無機相は次に電解質の初期濃度
に調整したあと、次の電気分解工程へ再循環させた。有
機相の全部(317g)をNaOH(1%)100gで
洗って真空蒸留した。これにより、OCB112gが未
反応OCTおよび残留物から分離された。OCTのOC
Bへの転化率は81.1%であり、Mn3+のOCTへの
転化率は84.4%であった。After the reaction, the reaction mixture was transferred to a decantation flask in which the organic phase was separated from the inorganic phase by hot decanting for 1 hour. The separation efficiency was 99.0%. Thereafter, the inorganic phase was purified by stripping until the concentration of residual organic products was 400 ppm or less. The purified inorganic phase was then adjusted to the initial electrolyte concentration and then recycled to the next electrolysis step. All of the organic phase (317 g) was washed with 100 g of NaOH (1%) and distilled under vacuum. This separated 112 g of OCB from unreacted OCT and residue. OC of OC
The conversion to B was 81.1%, and the conversion of Mn 3+ to OCT was 84.4%.
【0024】同様の結果がOCTの代わりにp−クロロ
トルエン(PCT)を使用した場合にも得られた。Similar results were obtained when p-chlorotoluene (PCT) was used instead of OCT.
Claims (28)
酸化剤として第2の反応器の中で二価マンガン塩を電気
化学的に酸化することによって生成された三価のマンガ
ン塩を使用して、化学的に酸化することを特徴とするク
ロロベンズアルデヒドの製造方法。1. A chlorotoluene in a first reactor,
Chemically oxidizing a trivalent manganese salt produced by electrochemically oxidizing a divalent manganese salt in a second reactor as an oxidizing agent, wherein the chlorobenzaldehyde is chemically oxidized. Production method.
クロロトルエンでありそして製造されるクロロベンズア
ルデヒドがオルト−またはパラ−クロロベンズアルデヒ
ドである請求項1記載の方法。2. Chlorotoluene is ortho- or para-
A process according to claim 1 which is chlorotoluene and the chlorobenzaldehyde produced is ortho- or para-chlorobenzaldehyde.
ンでありそして製造されるクロロベンズアルデヒドがオ
ルトクロロベンズアルデヒドである請求項2記載の方
法。3. The method of claim 2 wherein the chlorotoluene is ortho-chlorotoluene and the chlorobenzaldehyde produced is ortho chlorobenzaldehyde.
である前記請求項のいずれかに記載の方法。4. The method according to claim 1, wherein the manganese salt anion is a sulfate anion.
る前記請求項のいずれかに記載の方法。5. The method according to claim 1, wherein the electrochemical oxidation step is performed in sulfuric acid.
範囲の濃度を有する硫酸中で実施される請求項5記載の
方法。6. The method of claim 5, wherein the electrochemical oxidation step is performed in sulfuric acid having a concentration ranging from 40 to 70%.
範囲の濃度を有する硫酸中で実施される請求項5記載の
方法。7. The method of claim 5, wherein the electrochemical oxidation step is performed in sulfuric acid having a concentration in the range of 50-60%.
の範囲の温度で実施される前記請求項のいずれかに記載
の方法。8. An electrochemical oxidation process at 70 to 100 ° C.
A method according to any of the preceding claims, carried out at a temperature in the range
範囲の温度で実施される請求項8記載の方法。9. The method according to claim 8, wherein the electrochemical oxidation step is performed at a temperature in the range of 85 to 95 ° C.
塩の濃度が電解質1リットルあたり2乃至6モルである
前記請求項のいずれかに記載の方法。10. The method according to claim 1, wherein the concentration of the total manganese salt during the electrochemical oxidation step is between 2 and 6 mol per liter of electrolyte.
塩の濃度が電解質1リットルあたり3乃至4モルである
請求項9記載の方法。11. The method according to claim 9, wherein the concentration of the total manganese salt during the electrochemical oxidation step is between 3 and 4 mol per liter of electrolyte.
ード材料とカソード材料が同種であって、ガラス質グラ
ファイト、鉛、鉛合金、プラチナ、パラジウムまたはル
テニウムでコーティングされたジルコニウム、またはパ
ラジウムまたはルテニウムでコーティングされたタンタ
ルである前記請求項のいずれかに記載の方法。12. The anode and cathode materials used in the electrochemical oxidation process are of the same type and are made of vitreous graphite, lead, lead alloy, platinum, palladium or ruthenium coated zirconium, or palladium or ruthenium. The method according to any of the preceding claims, which is a coated tantalum.
有する鉛合金である請求項12記載の方法。13. The method of claim 12, wherein the anode and cathode materials are silver-containing lead alloys.
したセル内で実施される前記請求項のいずれかに記載の
方法。14. The method according to any of the preceding claims, wherein the electrochemical oxidation step is performed in a cell with air dilution.
つくられた電解セル中で実施される前記請求項のいずれ
かに記載の方法。15. The method according to any of the preceding claims, wherein the electrochemical oxidation step is performed in an electrolytic cell made from an inert material.
複数の電解セルの電池中で実施される請求項15記載の
方法。16. The method of claim 15, wherein the electrochemical oxidation step is performed in a battery of a plurality of electrolytic cells arranged in parallel.
りそして良好な循環と脱ガスを保証する手段を具備して
いる請求項16記載の方法。17. The method of claim 16, wherein said plurality of electrolysis cells are of the bipolar type and include means for ensuring good circulation and degassing.
電流密度が200乃至700mA/cm2である前記請求項の
いずれかに記載の方法。18. The method according to claim 1, wherein the current density applied during the electrochemical oxidation step is between 200 and 700 mA / cm 2 .
電流密度が300乃至500mA/cm2である請求項18記
載の方法。19. The method of claim 18, wherein the current density provided during the electrochemical oxidation step is between 300 and 500 mA / cm 2 .
前記請求項のいずれかに記載の方法。20. The method according to any of the preceding claims, wherein the chemical oxidation step is performed in sulfuric acid.
囲の濃度を有する硫酸中で実施される請求項20記載の
方法。21. The method according to claim 20, wherein the chemical oxidation step is performed in sulfuric acid having a concentration ranging from 40 to 70%.
囲の濃度を有する硫酸中で実施される請求項21記載の
方法。22. The method according to claim 21, wherein the chemical oxidation step is performed in sulfuric acid having a concentration ranging from 45 to 60%.
範囲の温度で実施される前記請求項のいずれかに記載の
方法。23. The method according to any of the preceding claims, wherein the chemical oxidation step is performed at a temperature in the range of 80 to 110 ° C.
範囲の温度で実施される請求項23記載の方法。24. The method according to claim 23, wherein the chemical oxidation step is performed at a temperature in the range of 85 to 105 ° C.
濃度が酸化反応媒質1リットルあたり2乃至6モルであ
る前記請求項のいずれかに記載の方法。25. The method according to any of the preceding claims, wherein the concentration of the total manganese salt during the chemical oxidation step is between 2 and 6 mol per liter of oxidation reaction medium.
濃度が酸化反応媒質1リットルあたり3乃至4モルであ
る請求項25記載の方法。26. The method of claim 25, wherein the concentration of the total manganese salt during the chemical oxidation step is between 3 and 4 moles per liter of the oxidation reaction medium.
ヒドへの転化の選択性を最大にしそしてクロロ安息香酸
の生成を最少にするために、約30乃至50%の転化率
が達成された時にクロロトルエンのクロロベンズアルデ
ヒドへの転化を中断する前記請求項のいずれかに記載の
方法。27. To maximize the selectivity of the conversion of chlorotoluene to chlorobenzaldehyde and to minimize the production of chlorobenzoic acid, the chlorotoluene aldehyde of chlorotoluene is obtained when a conversion of about 30 to 50% is achieved. A method according to any of the preceding claims, in which the conversion to H2 is interrupted.
的酸化工程の反応生成物混合物から分離する分離操作を
カラム抽出装置を使用して実施し;そして有機相をアル
カリ洗浄の処理にかけて痕跡量の硫酸を除去し、そのあ
と蒸留してクロロベンズアルデヒド生成物を未反応クロ
ロトルエンから分離し、その未反応クロロトルエンはそ
のあと化学的酸化工程に再循環される前記請求項のいず
れかに記載の方法。28. A separation operation which separates the desired chlorobenzaldehyde from the reaction product mixture of the chemical oxidation step is performed using a column extractor; and the organic phase is subjected to an alkaline wash to remove traces of sulfuric acid. A process according to any of the preceding claims, wherein the chlorobenzaldehyde product is subsequently separated by distillation from unreacted chlorotoluene, which unreacted chlorotoluene is then recycled to the chemical oxidation step.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9714275.6A GB9714275D0 (en) | 1997-07-08 | 1997-07-08 | Oxidation process |
GB9714275.6 | 1997-07-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH1180069A true JPH1180069A (en) | 1999-03-23 |
Family
ID=10815470
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10192208A Pending JPH1180069A (en) | 1997-07-08 | 1998-07-08 | Oxidation |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0890566A1 (en) |
JP (1) | JPH1180069A (en) |
GB (1) | GB9714275D0 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20140124341A (en) * | 2013-04-16 | 2014-10-24 | 롬 앤드 하스 일렉트로닉 머트어리얼즈 엘엘씨 | Chrome-free methods of etching organic polymers with mixed acid solutions |
JP2015518083A (en) * | 2012-01-23 | 2015-06-25 | マクダーミッド アキューメン インコーポレーテッド | Etching of plastic using acidic solution containing trivalent manganese |
CN105209667A (en) * | 2013-03-12 | 2015-12-30 | 麦克德米德尖端有限公司 | Electrolytic generation of manganese (III) ions in strong sulfuric acid |
JP2016504492A (en) * | 2012-11-15 | 2016-02-12 | マクダーミッド アキューメン インコーポレーテッド | Electrolytic production of manganese (III) ions in concentrated sulfuric acid |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9752241B2 (en) | 2012-01-23 | 2017-09-05 | Macdermid Acumen, Inc. | Electrolytic generation of manganese (III) ions in strong sulfuric acid using an improved anode |
US9534306B2 (en) | 2012-01-23 | 2017-01-03 | Macdermid Acumen, Inc. | Electrolytic generation of manganese (III) ions in strong sulfuric acid |
CN106621695B (en) * | 2016-11-21 | 2020-11-10 | 湖北绿色家园材料技术股份有限公司 | Method for treating and recycling tail gas generated in benzaldehyde production |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR207228A1 (en) * | 1973-08-01 | 1976-09-22 | Oxy Metal Industries Corp | A METHOD OF PRODUCING P-SUBSTITUTE BENZALDEHYDE |
JPS58502027A (en) * | 1981-11-23 | 1983-11-24 | バロ−ス・コ−ポレ−ション | Peripherals adapted to monitor low data rate serial input/output interfaces |
GB2140034B (en) * | 1983-05-18 | 1986-07-09 | Electricity Council | Electrolytic oxidation of manganous ion |
-
1997
- 1997-07-08 GB GBGB9714275.6A patent/GB9714275D0/en active Pending
-
1998
- 1998-06-30 EP EP98810606A patent/EP0890566A1/en not_active Withdrawn
- 1998-07-08 JP JP10192208A patent/JPH1180069A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015518083A (en) * | 2012-01-23 | 2015-06-25 | マクダーミッド アキューメン インコーポレーテッド | Etching of plastic using acidic solution containing trivalent manganese |
JP2016504492A (en) * | 2012-11-15 | 2016-02-12 | マクダーミッド アキューメン インコーポレーテッド | Electrolytic production of manganese (III) ions in concentrated sulfuric acid |
CN105209667A (en) * | 2013-03-12 | 2015-12-30 | 麦克德米德尖端有限公司 | Electrolytic generation of manganese (III) ions in strong sulfuric acid |
KR20140124341A (en) * | 2013-04-16 | 2014-10-24 | 롬 앤드 하스 일렉트로닉 머트어리얼즈 엘엘씨 | Chrome-free methods of etching organic polymers with mixed acid solutions |
Also Published As
Publication number | Publication date |
---|---|
GB9714275D0 (en) | 1997-09-10 |
EP0890566A1 (en) | 1999-01-13 |
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